EP2969326A1 - Method of joining sintered parts of different sizes and shapes - Google Patents
Method of joining sintered parts of different sizes and shapesInfo
- Publication number
- EP2969326A1 EP2969326A1 EP14717872.7A EP14717872A EP2969326A1 EP 2969326 A1 EP2969326 A1 EP 2969326A1 EP 14717872 A EP14717872 A EP 14717872A EP 2969326 A1 EP2969326 A1 EP 2969326A1
- Authority
- EP
- European Patent Office
- Prior art keywords
- parts
- sintered
- cemented carbide
- sintered parts
- assembled
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Withdrawn
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
- B23P15/28—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass cutting tools
- B23P15/32—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass cutting tools twist-drills
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F7/00—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression
- B22F7/06—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools
- B22F7/062—Manufacture of composite layers, workpieces, or articles, comprising metallic powder, by sintering the powder, with or without compacting wherein at least one part is obtained by sintering or compression of composite workpieces or articles from parts, e.g. to form tipped tools involving the connection or repairing of preformed parts
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B51/00—Tools for drilling machines
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B51/00—Tools for drilling machines
- B23B51/02—Twist drills
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B51/00—Tools for drilling machines
- B23B51/06—Drills with lubricating or cooling equipment
-
- C—CHEMISTRY; METALLURGY
- C22—METALLURGY; FERROUS OR NON-FERROUS ALLOYS; TREATMENT OF ALLOYS OR NON-FERROUS METALS
- C22C—ALLOYS
- C22C29/00—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides
- C22C29/02—Alloys based on carbides, oxides, nitrides, borides, or silicides, e.g. cermets, or other metal compounds, e.g. oxynitrides, sulfides based on carbides or carbonitrides
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F5/00—Manufacture of workpieces or articles from metallic powder characterised by the special shape of the product
- B22F2005/001—Cutting tools, earth boring or grinding tool other than table ware
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
- B23B2222/16—Cermet
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2222/00—Materials of tools or workpieces composed of metals, alloys or metal matrices
- B23B2222/28—Details of hard metal, i.e. cemented carbide
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2250/00—Compensating adverse effects during turning, boring or drilling
- B23B2250/12—Cooling and lubrication
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23B—TURNING; BORING
- B23B2250/00—Compensating adverse effects during turning, boring or drilling
- B23B2250/16—Damping of vibrations
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B23—MACHINE TOOLS; METAL-WORKING NOT OTHERWISE PROVIDED FOR
- B23P—METAL-WORKING NOT OTHERWISE PROVIDED FOR; COMBINED OPERATIONS; UNIVERSAL MACHINE TOOLS
- B23P15/00—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass
- B23P15/28—Making specific metal objects by operations not covered by a single other subclass or a group in this subclass cutting tools
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T408/00—Cutting by use of rotating axially moving tool
- Y10T408/44—Cutting by use of rotating axially moving tool with means to apply transient, fluent medium to work or product
- Y10T408/45—Cutting by use of rotating axially moving tool with means to apply transient, fluent medium to work or product including Tool with duct
- Y10T408/458—Cutting by use of rotating axially moving tool with means to apply transient, fluent medium to work or product including Tool with duct including nozzle
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T408/00—Cutting by use of rotating axially moving tool
- Y10T408/89—Tool or Tool with support
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T408/00—Cutting by use of rotating axially moving tool
- Y10T408/89—Tool or Tool with support
- Y10T408/909—Having peripherally spaced cutting edges
- Y10T408/9095—Having peripherally spaced cutting edges with axially extending relief channel
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
- Y10T—TECHNICAL SUBJECTS COVERED BY FORMER US CLASSIFICATION
- Y10T408/00—Cutting by use of rotating axially moving tool
- Y10T408/89—Tool or Tool with support
- Y10T408/909—Having peripherally spaced cutting edges
- Y10T408/9095—Having peripherally spaced cutting edges with axially extending relief channel
- Y10T408/9097—Spiral channel
Definitions
- the present disclosure relates to a method of joining different sized and/or shaped parts or members to form a unitary body, and more particularly, to a method for joining sintered parts of different sizes and/or shapes to form a unitary tool or wear part.
- High wear resistant materials such as cemented carbide, are popular for rock and metal drilling tools and for wear parts. Bodies of these materials are usually made by powder metallurgical methods, namely, pressing and sintering.
- a multi-member cemented carbide body can be independently formed of distinct green bodies.
- the independently formed green bodies are also independently sintered and, sometimes after grinding, assembled, for example, by soldering, brazing, direct pressing or shrink fitting to form a multiple- region cemented carbide body.
- the desired form of the sintered body is usually obtained before sintering after which the partial bodies are sintered together to form a body with a desired, often complex geometry, because machining of the sintered body is expensive.
- independently formed bodies are assembled and then sintered.
- the different combinations of the same ingredients that comprise the independently formed bodies respond to sintering differently.
- Each combination of ingredients responds uniquely to a sintering temperature, time, atmosphere or any combination of the proceeding and thus shrinks uniquely.
- U.S. Patent No. 6,908,688 also discloses the use of superatmospheric to form a hard metal tool having different joined bodies, in this and in the other known methods significant migration of the constituents across the boundary of the parts occurs. This can lead to precipitation of embrittling phases and long gradient zones of intermediate properties, causing, in severe cases, large scale density changes and consequent distortion of the parts.
- a method of joining a plurality of parts to form a unitary body includes the steps of providing at least two sintered parts, each of the parts being formed of a cemented carbide or cermet, at least one of the sintered parts having at least one internal channel.
- the at least two sintered parts are assembled into a shape of a unitary body, wherein each of the at least two parts has a joining surface and when each joining surface is brought into contact the joined surfaces form a bonding interface therebetween.
- the assembled at least two parts are subjected to a vacuum or gas atmosphere, without the application of external pressure, and to a temperature sufficient to fuse the at least two sintered parts together at the bonding interface to form the unitary body.
- a wear resistant tool in another aspect includes a plurality of sintered parts, At least one of the plurality of sintered parts has at least one internal channel.
- Each of the plurality of sintered parts is formed of a cemented carbide or cermet, wherein the plurality of sintered parts can be assembled into a shape of a unitary body.
- a joining surface is disposed on each of the plurality of sintered parts, wherein when the parts are assembled each joining surface is brought into contact to form a bonding interface therebetween, such that when the assembled parts are subject to a vacuum or gas atmosphere, without the application of external pressure, and to a temperature sufficient to fuse the plurality of parts, the plurality of parts are joined together at a respective bonding interface to form the unitary body.
- Fig. 1 is a flow diagram illustrating the steps of the present method.
- FIG. 2A is a perspective view of still another body made according to the present method.
- Fig. 2B is an end view of the body of Fig. 2A.
- Fig. 2C is a cross-sectional view of the body taken along line 1-1 of Fig. 2A.
- FIG. 3A is a perspective view of still another body made according to the present method.
- Fig. 3B is an end view of the body of Fig. 3A.
- Fig. 3C is a cross-sectional view of the body taken along line II-!I of Fig. 3A.
- a method of bonding or joining at least a pair of parts is described.
- a plurality of parts 32 and 34 are provided.
- the parts can be of the same size or shape or different sizes or shapes. It should also be appreciated that numerous parts can be joined according to the present disclosure, which should not be limited to a particular number of parts used to form a unitary body 30.
- a unitary body is defined as a singular body of connected parts.
- body 30 can be a wear resistant tool such as a step drill having different diameter parts.
- Parts 32 and 34 can be made from cemented carbide or cermet of compacts of liquid phase sintered materials which include low melting phase components and high melting phase components.
- a cemented carbide has a hard phase composed of tungsten carbide and of one or more carbides, nitrides or carbonitrides of titanium, chromium, vanadium, tantalum, niobium bonded by a metallic phase typically cobalt, nickel, iron or combinations thereof in varying proportions.
- a cermet has a hard phase composed of one or more carbides, nitrides or carbonitrides of titanium, chromium, vanadium, tantalum, niobium bonded by a metallic phase typically cobalt, nickel, iron or combinations thereof in varying proportions
- Cermet and cemented carbides exist in different grades. Grade refers herein to a cemented carbide or cermet, in one of several proportions and with a certain grain size. The performance and reliability of the grades depends on the composition of the cermet and the cemented carbide. A high quality grade is a material with a quantifiably greater performance and reliability in a given application.
- the parts can be cemented carbide of the same composition, or two or more different compositions and being different with respect to grade and/or grain size that are fused together, as will be described further herein.
- Each part has been sintered for obtaining substantially the full density and hardness thereof. See step 14.
- Each part has a joining surface 38.
- the parts are ground or machined at the mating/joining surfaces to provide a sufficiently smooth finish between the parts.
- the parts can also be cleaned, for example, in a hydrogen cleaning process, to provide a clean interface at the joining surfaces.
- the individual, parts are assembled into the desired tool shape in step 18.
- Step 20 involves bringing the parts into contact in an assembled relationship with a first bonding or joining surface 38 between two of the parts in mating engagement with a second bonding or joining surface between the other of the parts to each define a bonding or boundary zone 36. Thereafter, the step of heating the parts in the assembled relationship is employed to fuse the parts together,
- step 20 the parts are fused at a temperature low enough so that no grain growth occurs. For example, of about 1340°C to about 1360°C for about 10 to about 30 minutes, and more preferable about 1350°C for about 15 minutes.
- the parts are fused at a temperature lower than or intermediate to the melting point of the cemented carbide having the lowest original sintering temperature of the parts. This lower temperature and shorter time enables the fusing to proceed by short range diffusion of the binder metals across the interface and no grain size changes are induced in the microstructures,
- This step takes the already dense and hard piece of carbide and puts it back into the sintering furnace. But, instead of getting shrinkage and a more density, as in the first sintering operation, the part remains essentially the same in physical properties. The minimal amount of liquid phase possible occurs, but still bonding is enabled to take place.
- the present method enables joining of sintered parts having different sizes and shapes to form a unitary tool or wear part.
- tool 30 is described in this example, it should be appreciated that, and as shown in the following example, a body comprised of different material, sized or shaped parts can be made according to the present method. Accordingly, the sizing and/or shaping of the members are a function of the particular unitary body or tool desired and the particular physical and/or dimensional characteristics are therefor according to satisfactorily meet an intended use.
- Different grade materials can be joined to optimize local properties of, for example, the tool or wear part.
- wear resistance, toughness, brazability, friction coefficient and/or cubic boron nitride (cBN) content of a material can be chosen depending on the location of the material in the tool or wear parts.
- a cobalt or grain-size mismatch can also be chosen to induce binder metal fusing and consequent density changes. This can induce compressive stresses at the tool or part surfaces to provide a toughening effect.
- multilayers having large cobalt content or grain size mismatch can be incorporated for crack deflection.
- the present methodology allows for pre-shaping of grooves, channels or holes at the interface of the fused parts allowing cooling channels to be constructed.
- the tool or wear part 30 has a plurality of internal coolant channels for applications where the coolant flows internally within the parts so no coolant contact with the material is desired. This feature allows the work environment to be kept clean and easy to recycle.
- body 32 has a feeder channel 40 that extends down the center of the body.
- a plurality of helical channels/holes 42 extend along the length of the tool Coolant flows through feeder channel 40 and out through the helical channels 42, Helical channels 42 are blocked by part or point 34 that is fused to body 32 at boundary zone 38.
- a drill 50 has a body or shank 52 and an end part or tip 54 fused at joining surfaces 56 and boundary zone 58 according to the present methodology.
- Body 52 has an internal coolant channel 60.
- Tip 54 has a plurality of coolant holes 62, the geometries of which can be machined in the tip prior to fusing.
- the tip blank can have the coolant holes 62 drilled into the blank while it is in a pre- sintered green state to produces holes at any angle and diameter.
- the disclosed method can be used to build complex shapes from a stock of different parts allowing for under cuts, side holes, voids, profile changes etc., but avoiding MAP/PIM or machining.
- any of the above features can be combined in a single tool or part. For example, different parts can be carefully selected and joined together to suit particular applications where wear, chemical resistance, etc. is required.
- the present methodology offers many advantages, included but not limited to, significant cost savings and environmentally friendly production. Key advantages also include formation of complex shapes not possible by conventional processing or machining. Also material combinations not possible by current methods can be achieved.
Landscapes
- Engineering & Computer Science (AREA)
- Mechanical Engineering (AREA)
- Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Composite Materials (AREA)
- Manufacturing & Machinery (AREA)
- Metallurgy (AREA)
- Organic Chemistry (AREA)
- Powder Metallurgy (AREA)
- Drilling Tools (AREA)
- Cutting Tools, Boring Holders, And Turrets (AREA)
- Pressure Welding/Diffusion-Bonding (AREA)
Abstract
Description
Claims
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US201361800836P | 2013-03-15 | 2013-03-15 | |
| PCT/IB2014/059798 WO2014141174A1 (en) | 2013-03-15 | 2014-03-14 | Method of joining sintered parts of different sizes and shapes |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| EP2969326A1 true EP2969326A1 (en) | 2016-01-20 |
Family
ID=50489359
Family Applications (3)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14717870.1A Withdrawn EP2969324A1 (en) | 2013-03-15 | 2014-03-14 | Method of joining sintered parts of different sizes and shapes |
| EP14717871.9A Withdrawn EP2969325A1 (en) | 2013-03-15 | 2014-03-14 | Method of joining sintered parts of different sizes and shapes |
| EP14717872.7A Withdrawn EP2969326A1 (en) | 2013-03-15 | 2014-03-14 | Method of joining sintered parts of different sizes and shapes |
Family Applications Before (2)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| EP14717870.1A Withdrawn EP2969324A1 (en) | 2013-03-15 | 2014-03-14 | Method of joining sintered parts of different sizes and shapes |
| EP14717871.9A Withdrawn EP2969325A1 (en) | 2013-03-15 | 2014-03-14 | Method of joining sintered parts of different sizes and shapes |
Country Status (6)
| Country | Link |
|---|---|
| US (4) | US9498824B2 (en) |
| EP (3) | EP2969324A1 (en) |
| JP (4) | JP6453253B2 (en) |
| KR (3) | KR102210170B1 (en) |
| CN (3) | CN105102162B (en) |
| WO (3) | WO2014141174A1 (en) |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| US9498824B2 (en) * | 2013-03-15 | 2016-11-22 | Sanfvik Intellectual Property Ab | Method of joining sintered parts of different sizes and shapes |
| MX390167B (en) * | 2014-03-14 | 2025-03-20 | Hyperion Materials & Tech Sweden Ab | COMPOSITE ROLL. |
| KR20190016142A (en) * | 2014-06-12 | 2019-02-15 | 알파 어?블리 솔루션 인크. | Sintering materials and attachment methods using same |
| US10010948B1 (en) * | 2014-10-14 | 2018-07-03 | Matthew W. Hayden | Near-net shaped cutting tools and processes and devices for making the same |
| JP6380016B2 (en) * | 2014-11-05 | 2018-08-29 | 株式会社タンガロイ | Cermet tools and coated cermet tools |
| FR3039266B1 (en) * | 2015-07-22 | 2017-09-01 | Cime Bocuze | PENETRATOR HAVING A CORE SURROUNDED BY A DUCTILE SHEATH AND METHOD FOR MANUFACTURING SUCH A PENETRATOR |
| IL246227B (en) * | 2016-06-15 | 2021-07-29 | Hanita Metal Works Ltd | Channeled Cutting Tool Configuration and Method Therefor |
| CN106583806A (en) * | 2016-11-11 | 2017-04-26 | 丹阳宝联五金制品有限公司 | Combined ceramic drill bit |
| EP3372330B1 (en) * | 2017-03-10 | 2023-01-04 | Seco Tools Ab | Tool tip |
| AT16076U1 (en) * | 2017-03-14 | 2018-12-15 | Ceratizit Austria Gmbh | Tool body and a method of manufacture |
| DE102017205166B4 (en) | 2017-03-27 | 2021-12-09 | Kennametal Inc. | Modular rotary tool and modular tool system |
| DE102017212054B4 (en) | 2017-07-13 | 2019-02-21 | Kennametal Inc. | Method for producing a cutting head and cutting head |
| US11142959B2 (en) | 2017-07-28 | 2021-10-12 | Baker Hughes Oilfield Operations Llc | Rotatable cutters and elements for use on earth-boring tools in subterranean boreholes, earth-boring tools including same, and related methods |
| US10697247B2 (en) | 2017-07-28 | 2020-06-30 | Baker Hughes, A Ge Company, Llc | Rotatable cutters and elements for use on earth-boring tools in subterranean boreholes, earth-boring tools including same, and related methods |
| US10851592B2 (en) | 2017-07-28 | 2020-12-01 | Baker Hughes | Movable cutters and devices including one or more seals for use on earth-boring tools in subterranean boreholes and related methods |
| KR101996367B1 (en) | 2017-10-23 | 2019-07-03 | 주식회사 동남케이티씨 | Support device for tungsten cobalt sintered product bonding |
| US10619421B2 (en) | 2017-11-13 | 2020-04-14 | Baker Hughes, A Ge Company, Llc | Methods of forming stationary elements of rotatable cutting elements for use on earth-boring tools and stationary elements formed using such methods |
| US10562109B2 (en) * | 2017-11-22 | 2020-02-18 | The Boeing Company | Tapered drill bit and automated process |
| EP3488952B1 (en) * | 2017-11-24 | 2024-03-13 | Seco Tools Ab | A method for manufacturing a tool head |
| DE102018202941B4 (en) | 2018-02-27 | 2024-01-25 | Kennametal Inc. | Process for producing a blank from extrusion mass and extruder |
| EP3533545A1 (en) * | 2018-03-01 | 2019-09-04 | AB Sandvik Coromant | Modular cutting tool body and method for manufacturing the same |
| AT16369U1 (en) * | 2018-03-12 | 2019-07-15 | Ceratizit Austria Gmbh | Process for producing a sintered composite body |
| CN112077370B (en) | 2019-06-13 | 2024-10-01 | 肯纳金属印度有限公司 | Indexable drill insert |
| CN111215631B (en) * | 2020-03-16 | 2020-12-25 | 济南市冶金科学研究所有限责任公司 | Tungsten-cobalt hard alloy product thermal connection method |
| DE102021116316A1 (en) * | 2020-07-08 | 2022-01-13 | Transportation Ip Holdings, Llc | PROCESS AND SYSTEM FOR EQUIPMENT MANUFACTURE |
| CN115703157A (en) | 2021-08-17 | 2023-02-17 | 肯纳金属印度有限公司 | Indexable drill assembly with coolant system |
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Also Published As
| Publication number | Publication date |
|---|---|
| US20140260808A1 (en) | 2014-09-18 |
| US20140271003A1 (en) | 2014-09-18 |
| KR102210170B1 (en) | 2021-01-29 |
| JP2019035152A (en) | 2019-03-07 |
| KR20150127685A (en) | 2015-11-17 |
| CN105102162B (en) | 2018-11-13 |
| JP2016516130A (en) | 2016-06-02 |
| KR20150127686A (en) | 2015-11-17 |
| WO2014141172A1 (en) | 2014-09-18 |
| KR20150127687A (en) | 2015-11-17 |
| CN105121073A (en) | 2015-12-02 |
| JP6453253B2 (en) | 2019-01-16 |
| WO2014141174A1 (en) | 2014-09-18 |
| CN105142828B (en) | 2017-10-24 |
| JP6453254B2 (en) | 2019-01-16 |
| CN105142828A (en) | 2015-12-09 |
| JP6591021B2 (en) | 2019-10-16 |
| EP2969325A1 (en) | 2016-01-20 |
| US10265813B2 (en) | 2019-04-23 |
| US20170036311A1 (en) | 2017-02-09 |
| US9498824B2 (en) | 2016-11-22 |
| US20140271008A1 (en) | 2014-09-18 |
| KR102210176B1 (en) | 2021-01-29 |
| EP2969324A1 (en) | 2016-01-20 |
| JP2016516132A (en) | 2016-06-02 |
| JP2016516131A (en) | 2016-06-02 |
| WO2014141173A1 (en) | 2014-09-18 |
| CN105102162A (en) | 2015-11-25 |
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